Monocyclic aminobenzene compounds containing fluorine



Patented July 25, 1950 UNITED STA-rel (PATENT OFFICE 2,516,107 MoNooYoLIc AMINOBENZENE COMPOUNDS CONTAINING FLUORINE Joseph B. Dickey, Rochester, N.Y.', assignor to 1 Eastman Kodaki Co'mpany, Rochester, Y1, a

corporationof New Jersew No Drawing-.7.- Application October 26, 1945*,

Serial No. 624,943

3 "Claims. (Cl. 260-f573)" This "-inventionrela'tes "to monocyclic'aminm can. be prepared :by reacting a :-chlorobenzene,.-: benzene compoundscontaining anuclear amino compound :with. a ."idifluoroalkylaminear If .degroup whichis substituted wiiilflanaliitil'latic hysired'a catalyst for-the reaction suchas'powdered drocarbon groumhayinga difluorinatedmcarbonA., copper and -cuprous oxide camberem-ployedr Th atom. aminobenzene compounds of the inventiontcami. The compoundsoflmy inventionconstitute vale alsosbe reparedby reaction between an amino.

rdye.intermediates being llSefULimmOShine y benzeneland. a difluoroalkanol inthepresence o stances as coupling zcomponents-forathe preparaa metallic hydrogenation catalyst, such as "Ramnm tion of azo dyes. They:are. .also usef-ul -eforthe e nickel and other nickel catalysts-,a cobalt cata-jew production f intermediates f r lor p elyst .and. copperchromite. 'Astill furthermethod g raphys It" is an" object of myinven mn p by which the compounds 'ofrtherinvention can thes vide. new-.monocyclic. aminobenzene compounds preparednis by reaction-between-ranaminobenw containing.,.fluorine. Another :Object of my in.-- zene compound and a difluoroalkyl' halide-.in=-thee,-. vention- .is.,to..providel: new ramiriobenzenercomrn presence of an acid binding agent. Acid bindpoundsl-containing;fluorineawhichflare-iuseiul,jas. 'ing agents that canbe used include; for example,. dye intermediatesand fonthe production of in sodiumparbonate;potassium carbonatersodium termediateslior. color.aphotography,v Aiurthen, hydroxide, potassium hydroxide, sodium '"bicar object is.to provideasatisfactory process,..for the; bonate, potassiumbicarbonate" and -bariu'mhy'-'"- preparation ofthenew,aminobenzenecompounds. droxide. Each of these methods of preparatio'nris containing fluorine. illustrated hereinafter.

While my invention relates broadly to mono- Difluoroalkylamines "that 'carnbe used*'in *th"e"* cyclic -aminobenzcnecompounds containing a preparation of the compounds of my-iriventidn nuclear amino groupt'which is substituted with include, for example; 2,2 difiuoroethylamine" an aliphatic hydrocarbon group having a difiuo- M (CHFz'CHNI-IQ} cr- (2,2 diflu0ro)=die'thyljamine rinated carbon atom, it relates. more" particularly (CI-IFzCHzMNH/ 2,2}=difilio1 0"- n-- propylam-ine 1J0 m clic aminobenzene compounds c0ntain- (CI-I3CF2CH2NH2)and-3;3 difluoro n butylamine 5' ing a nuclear amino r upwhi h is substituted. (CI-IaOFzCI-IzGI-I'zNHz).Difluoroalkyl halides tliata with a"1OW car n al p a ydr carb rrsroup" can be employe'd 'include,- for examplepBr'CHFQw having 'a "difiuorinated carbon-atom:- By'afloiw ClCEZFl ,v C1CH2CHF2,.-- BrCI-IzCI-IEaw. ICHZCHEQ carbonialiphatic hydrocarbon groupismeant one "3Oc 1c 1- and C1CH2CH2CF2CH3' Diiiuorocontaining 5 13;) 4 cairb'mfatfimsf 57 alkanol compounds, that can be employed include, thenucle'ar amin srnupw ll 'su for example, 2,2-difluoroethanolKCHFzCHzOI-I). a '-'d fl $7 (CH2CI-IF2) f g io ifli In the interest-of. simplicity; the term.difluoro.-. p u d ih'avin t n lrf r u ethyl-13s frequently used throughout the specifica R 'fi tionainstead of..2,2-..difluoroethyl. Itwill .benunag derstoodthatrwhenever. the term'..difiuoroethyl;isw

used herein, 2,2-.difiuoroethyl is intended. Thei following -examplesillustrate:- the 00mm pounds ofv my. inventioniand'. the process. used to. wherein R is hydrogenlor an aliphatic group, A 4 q,.,, is a low carbon aliphatic hydrocarbon group v I, having a difluorinated carbon atom X is a low Emmple (-2,2-dzfluoroethyl)'-amlme carbon alkyl groupraloW carbonalkoxy group, a H halogen atom or a low carbon aliphaticacyl- GN GHZOHFQ aminorgroupz'and n-"is:.0;' 1 orv'2 appearrtd'be adei vantageous 28 grams ofchlorobenzene, 81 grams of2, 2 di"-' The nuclear: aminoigroupi ofiiithe monocyclic'r. fluoroethylamine, 3 f w r; 0.25 gram ofaminobenzene compound' carrrbe substituted with? copp p fi gram D ZOHS d -i" eithei one orutwo-aliphatic.hydrocarbongroups. are heated togetherrina c pp d' s fl ing-ifi having carbon tom .whi' hj'ig' diflfibriflatd. autoclave at220-.225:=- C;ior ae hourswith'asha n Normally, only one such"alifih'atic group will be ing. When cool, the contents for the autoclave... present. Where two such aliphatic groups are are removedandextracted with benzene. After present, they can be the same groupjlor different drying, the benzene eXtractjis fractionally disgroups. tilled under reducedpr'essure to recover N-(2,2- The aminobenzene compounds oifcthe invention w difluoroethyl) aniline and'unreacted '2,2-difluoroethyl-amine N-(2,2-difluoroethyl) aniline is a colorless liquid.

Using the procedure described in Example 1 and employing the "proper chlorobenzene compound, the following compounds are readily prepared: r

N-difiuoroethyl-o-toluidine N-difluoroethyl-o-ethylaniline N-difluoroethyl-o-anisidine N-difluoroethyl-m-toluidine I N-difluoroethyl-m-anisidine N -difiuoroethyl 2 methoxy, methylaniline N-difluoroethy1-2-methoxy-5 acetaminoaniline N-difluoroethyl-3-acetaminoaniline By the use of 2,2-difluoro-n-propylami-ne, 3,3-

ethylamine, respectively, in place of 2,2-difluoroethylamine in Example 1, N-(2,2-difluoro-n-propyl) -aniline, N-(3,3-difluoro n butyl) -aniline and N,N-di( 2,2-difluoroethyl) -aniline, respectively, areobtained. It will be understood that by the'use of these amines, other aniline compounds containing a 2,2-difiuoro-n-propyl group, a, 3,3- diflu'oro-n-butyl group or two 2,2-difluoroethyl groups on the nuclear amino group can be prepared. 'o-Toluidine, o-ethylaniline, o-anisidine, m-toluidine, m-anisidine, 2-methoxy-5-methylaniline, 2-meth0xy-5-acetaminoaniline, m-acetaminoaniline and m-propionylaminoaniline, for example, are illustrative of the aniline compounds that may be so substituted. Thus, the following compounds can be prepared:

N- 2,2-difiuoro-n-propyl) -o-toluidine N-(2,2-difluoro-n-propyl) -2-methoxy-5-methylaniline N-(2,2-difluoro n propyl)-m-propionylaminoaniline N- (2,2-difiuoro-n-propyl) -m-toluidine N-(3,3-difluoro-n-butyl) 2 methoxy 5 acetaminoaniline N- 3 ;3-difluoro-n-butyl) -o-anisidine N- (3,3-difluoro-n-butyl) -m-acetaminoaniline N-(3,3-difluoro-n-butyl) -o-ethylaniline N,N-di- (2,2-difiuoroethyl) -aniline N,N-di- (2,2-difluoroethyl) -m-t0luidine N,N-di- (2,2-difluoroethyl) -mchloraniline Example 2.-N-(2,2-difluoroethyl) -4-nitroaniline N- (2,2-difiuoro-n-propyl) -4-nitroaniline N-(3 ,3-difiuoro-n-butyl) -4-nitroaniline N,N-di- (2,2-difiuoroethyl) -4-nitroaniline Example 3.N- (2,2-difluoroethyl) -p-phenylenediamine This compound is prepared by reducing N 2,2- difluoroethyl) -4-nitroaniline. The reduction can be carried out with tin and hydrochloric acid or more preferably with hydrogen under pressure in the presence of a catalyst such as Raney nickel. Similarly, the following compounds can be prepared:

N- (2,2-difluoro-n-propyl) -p-phenylenediamine 'N- (3,3-difiuoro-n-butyl) -p-phenylenediamine N ,N-di- 2 ,2 -difluoroethyl) -p-phenylenediamine Example 4.-N- (2,2-olifluoroethyl) -m-toluidine 47 grams of m-toluidine, '74 grams of 2,2-difiuoroethanol and 5 grams of Rane nickel are heated together in a shaking autoclave for 25 hours. When cool, the contents of the autoclave are removed and filtered to remove nickel and the filtrate is fractionated under reduced pressure (6 mm., for example). N-(2,2difiuoroethyl) -m-toluidine is obtained in a good yield.

Using the procedure described in Example 4,

the following compounds are readily prepared:

N-(2,2-difluoroethyl) -o-chloroaniline N- (2,2-difiuoroethyl) -o-anisidine I N- (2,2-difluoroethyl) -m chloroaniline N -(2,2-difiuoroethyl) -m-n-butyrylaminoaniline N- (2,2-difiuoroethyl) -2,5-dimethoxyaniline N (-2,2-difluoroethyl -ariiline.

Example 5.N- (2,2-difluoroethyl) -o-anisidine 15 grams of 2,2-difluoroethylbromide, 12 grams of o-anisidine and 6 grams of sodium carbonate are placed in a suitable reaction vessel and heated under refluxing conditions until carbon dioxide ceases to be evolved. Upon cooling, the reaction mixture is extracted with ethyl alcohol and the ethyl alcohol extract is fractionated under reduced pressure to give a good yield of N-gaz-di fluoroethyl) -o-anisidine.

Example 6.N,N-di-(fluoroethyl) -'rn-tolm'dine omoHFi 17 grams of N-difiuoroethyl-m toluidine, 15-" grams of difluoroethylbromide and 6 grams of sodium carbonate are placed in a suitable reaction vessel and heated under refluxing conditions until carbon dioxide ceases to be evolved. The reaction product is extracted with ethyl alcohol and the ethyl alcohol extract is fractionated under reduced pressure (5 mm., for example) to give a good yield of N,N-di-(difiuoroethyl)-mtoluidine.

Example 7.-N-triflubroethyl'-N-difluoroethyl-mtoluidz'ne CHzCHFz OHICF;

This compound is obtained b reacting N-difluoroethyl-m-toluidine with 2,2,2-trifluoroethyl-= bromide (CFaCHzBr) in accordance with the procedure described in Example 6.

Example 8.-N-difluoromethyl-N-difluoroethyl- I m-toluz'dine C H F a r CHiCHFl This compound .is obtained by reacting N-di-' fluoroethyl-m-toluidine zwith 2,2-difl-i1oromethylbromide (ZBrCHFz) in accordance with the procedure described in Example 6.

rliollowing the procedure described in= Examples 5, 6, 7 and 8, the following compounds are'readi'ly prepared? N,N-di- (difluoromethyl) -aniline Nl N-di (d-i-fiuoromethyl) -m-toluidi-ne N,N-di- (difiuoroethyl) -ani1ine N,N- d-i- (difluoroethyD -m-chlor0aniline N,N-di- (difluoroethyl) -m-anisidine N;N-di- ('2;2-difiuoro-n-propyl) .-aniline N,N-di- (2,2-difluoro-n-propyl) -m-toluidine N,N-'di- (2;2 difiuoro-n-propyl) -m-fluoroaniline N,N-di- (3, 3-difiuoro-n-butyl) aniline N,N-di- (3',3 difluoro-n-buty1) -m-toluidine N,N-di- (3,3-difiuoro-n-butyl) -m-chloroaniline N'-difl-uoromethyl-N-difluoroethylaniline N-difiuoromethyl-N-difluoroethyl-m chloroani line N-difluoromethyl-N (2,2-difiuoro-n-propyl'). -aniline' N -difluoromethyl-N-( 2,2- -difiuoro-n-propyl) mtoluidine N-difluoromethyli-l-(2,2!difluoro-n-propyl) mbromoaniline N-difluoromethyl-N- (2,2-difluoro-n-propyl) .-2,5

' diethoxyaniline N-di-fiuoromethyl-N-(3,3-difiuoro-n-butyl) aniline i i N-difluoromethyl-N-(3,3-difiuoro n butyl) -mtoluidine N trifiuoroethyl-N- difiuoromethylaniline N'-trifluoroethyl-N-difluoromethyl-m propylaniline N-trifluoroethyl-N-difluoroethylaniline N-trifiuoroethyl N difiuoroethyl-o-toluidine N-tri'fluoroethyl-N difluoroethyl -m butoxyani line N#-(3,'33-trifluoropropyl) N difluoromethylaniline N (3;3-,3-trifluoropropyl) N difluor-omethyl-methylaniline N- (3,3,3-trifluoropropyl) -N-difiuoroethylaniline N- (3,3,3-trifiuoropropyl) -N-difluoroethyl-m toluidine N- (3,3,3-trifiuoropropyl) -N- (2,2-difiuoro-n propyl -ani1ine N-"(3,3,3'-trifluoropropyl) -N(3,3-difluoro-n bu tyl) -ani1ine N-4AA-trifiuorobut l) -l l-.difiuoromethy1aniline N- (MiA-trifluorobutyl) -N-difluoroethylaniline N-(4,4,4-trifiuorobutyl) -N-(2,2-difluoro n propyl) -aniline' N-(lgm-trifiuorobutyl) -1\T- (3,3-difluoro n -qbu a W ll-aniline N-B-methoxyethyl-N-difiuoroethylaniline N-.-fl-ethoxyethyleN-diiluoroethylan-il-ine Nepg-methoxyethyl-N-diiiuoroethyl-m-tollildine N;p-n ethoxyethy1-N- (3,3-difluoro-nbuty1') -aniline I i Compounds containing the 3,3,3-trifiuoropropyl (--CH2CH2CF3) group and the 4,4,4=-trifluorobutylv (*CH2CH2CH2CF3) group be prepared by using an equivalent gram molecular weight of OICHGI'IZ'CFs and .ClCHzCHzCI-IzCFa, respectively, in placeof the trifluoroethylbromide and difiuoromethylbromide compoundsof Examples '7 and .8

aniline 15.7 grams of N-difiuoroethylaniline, "5grams 6 of ethylene oxide and 50 cc. of dioxane are heated together with stirring in an autoclave at 180C. for six hours. Upon cooling, the reaction mixture is removed from theautoclave and distilled under reduced pressure. A good yield of N-fi-hydroxyethyl-Nrdifluoroethylaniline is obtained.

Using the procedure described in Example 9 and employing the proper alkylene oxide (trimethylene oxide, propylene oxide, glycidol, and B-methyl glycidol); the following compounds are readily prepared:

N-p hydroxypropyl-N-difiuoroethylaniline Iiiy-hydroxypropyl N-difluoroethylaniline N4? dihydroxypropyl-N-difiuoroethylaniline where a ,B -dihydroxypropyl group or other group which. Will decompose if the compound is attempted to be distilled is present, the reaction mixture is removed from the reaction vessel, filtered if desired and the solvent material removed by distillation under reduced pressure, leaving the desired product as a residue of the distillation.

m-chlo-roaniline 19.1 grams of N-difluoroethyl-m-chloroaniline, 5 grams of ethylene oxide and 50 cc. of dioxa-ne' are heated together with stirring in an autoclave at 180 C. for 6 hours. Upon cooling, the reaction mixture is removed from the autoclave and distilled under reduced pressure. A good yield of Np-hydroxyethyl-N-difluoroethyl-m chloroaniline is obtained.

Example 1 1.-- N-p,y-.dihydrowypropyl-N-difluorm ethyl-Z-methoxy- 5 -acetaminoaniline 24.4 grams of N-difluoroethyl-z-methoxy-5- acetaminoanilinev and 10.6 grams of sodium .carsbonate are mixed together and heated with stirring in a suitable reaction vessel in an atmosphere of nitrogen to G. Then 12 grams of glycerolchlorohydrin (C1CH2CHOI-ICH2OH) are added drop by drop with stirring over a period of three hours, while maintaining the temperature at 140 C. When'carbon dioxide ceases to be evolved, the

reaction mixture is extracted with acetic acid and the acetic acid extract is carefully fractionated under reduced pressure to remove the acetic acid. N-cp -dihydroxypr0py1 l\l-difluoroethyl-Z- methoxy-5-acetaminoaniline is obtained as a dark, viscous product and is stored in a stoppered bottle.

Where the intermediate is to be used as a coupling component in the preparation of azo dyes the fractionation operation may be omitted and the acetic acid extract stored and used as such,

If desired, the reaction mixture can be extracted with butyl alcohol and the desired product recovered by removing the butyl alcohol by'distillatioh or'evaporation.

17.1 grams of N-difluoroethyl-m-toluidine and 10.6 grams of sodium carbonate are mixed together and heated with stirring in a suitable reaction vessel in an atmosphere of nitrogen to 140 G. Then 12 grams of glycerol chlorohydrin are added drop by drop with stirring over a period of three hours, while maintaining the temperature at 140 C. When carbon dioxide ceases to beevolved, the reaction mixture is extracted with acetic acid and the acetic acid extract is carefully fractionated under reduced pressure mm., for example) to remove the acetic acid. N- {3,7 dihydroxypropyl N difiuoroethyl mtoluidine is obtained as a dark, viscous product and is stored in a stoppered bottle. If desired, the reaction product can be recovered by extraction with butyl alcohol as indicated above.

The process described in Examples 11 and 12 is broadly applicable. In place of the chlorohydrin used in the examples ethylene chlorohydrin, trimethylene chlorohydrin, ,6 methyl 5,7 dihydroxypropylchlorohydrin, propylene chlorohydrin and l-chloro-2,3,4-trihydroxybutane, for example, can be used to obtain compounds of the invention.

,Using the procedures described in Examples 9, 10, 11 and 12, the following compounds are readily prepared:

N- 5,7 dihydroxypropyl N difluoromethylm-chloroaniline N 4,5 dihydroxyamyl N difluoromethyl mtoluidine N p hydroxyethyl N difluoroethyl m toluidine N 3 hydroxyethyl N difiuoroethyl o to- -luidine N B hydroxyethyl N :difluoroethyl o anisidine N -:;3 hydroxyethyl N difluoroethyl m anisidine N p hydroxyethyl N difluoroethyl m bromoaniline N ,6 hydroxyethyl N difiuoroethyl m fluoroaniline N B hydroxyethyl N difiuoroethyl Z-methoxy-5-methylaniline N p? hydroxyethyl N difiuoroethyl 2-methoxy-5-acetaminoaniline N p hydroxyethyl N 3,3 difluoro n pro pylaniline N ,3 hydroxyethyl N 4,4 difluoro n-butylaniline N I3 hydroxypropyl N difiuoromethyl m- .toluidine N wk 5 hydroxypropyl N difluoroethyl m-toluidine N ,6 hydroxypropyl N difluoroethyl m-anisidine N p hydroxypropyl N difluoroethyl 2 methoxy-5-methylaniline N 13 hydroxypropyl N difluoroethyl 2,5-

dimethoxyaniline N c hydroxypropyl N difiuoroethyl 2-ethoXy-5-acetaminoaniline N hydroxypropyl N difluoroethyl mchloroaniline N 'y hydroxypropyl N difluoroethyl mtoluidine N Y hydroxypropyl N difluoroethyl 2- methoxy -5- chloroaniline N 'y hydroxypropyl N (2,2 difluoro npropyl) -aniline N 1 ,7 dihydroxypropyl N difiuoroethyl mbutyrylaminoaniline N 5,7 dihydroxypropyl N (2,2 difluoro npropyl) -aniline N [3,7 dihydroxypropyl N (3,3 difluoro-nbutyl) -aniline N 4,5 dihydroxyamyl N (2,2 difluoro npropyl) -aniline N 4,5 dihydroxyamyl N (3,3 difluoro nbutyl) -aniline N c methyl 5, dihydroxypropyl N (2,2-

difluoro-n-propyl) -aniline N {3 methyl [in dihydroxypropyl-N-(3,3-difluoro-n-butyl) --aniline N 2,3,4 trihydroxybutyl N difiuoroethylaniline N 2,3,4 trihydroxybutyl N (2,2-difluoro npropyl) -aniline N 2,3,4 trihydroxybutyl N (3,3-difluoro-nbutyl) -m-to1uidine Example 13.N {3 cyanoethyl N difluoroethylaniline 18 grams of N-difiuoroethylaniline, 30 grams of acrylonitrile and 2 cc. of sulfuric acid are placed in a suitable reaction vessel and heated on a. steam bath for several weeks. The sulfuric acid is then carefully neutralized by the addition of sodium hydroxide and the reaction mixture is fractionated under reduced pressure. A good yield of N-B-cyanoethyl-N-difluoroethylaniline is obtained.

Using the procedure described in Example 13, the following compounds are readily prepared: N 3 cyanoethyl N difluoroethyl m toluidine N 18 cyanoethyl N difluoroethyl m-chloroaniline N 5 cyanoethyl-N difluoroethyl 2 methoxy-5-methylaniline N ,dcyanoethyl N (2,2 difluoro n propyl) -aniline N ,6 cyanoethyl N (3,3-difluoro n butyl) aniline Example 14.Ethyl ester of N 13 carboxyethyl- N-difluoroethylaniline CHzCHFa mm., for example, to give a good yield of the ethyl ester of N-B-carboxyethyl-N-difiuoroethyl-' aniline.

Using the procedure described in Example 14, the following compounds are readily prepared:

Ethyl este of N-fl-carboxyethyl-N-difiuoroethyl m-toluidine Ethyl ester of N-fi-carboxyethyl-N-difluoroethylm-chloroaniline Ethyl ester of N-B-carboxyethyl-N-difluoroethyl- .m-fluoroam'line mas"! inrnyirester or11m earmxyetnyi wdmuoroetrfrlio-t'oluidine' i mthyl ester -dr-w peoarboxyetnymwz z-ilifluomn-prpyl)aniline" Ethyl ester of N-fi-carboxyethyl-N-(2;24dlflu0ron+propy1)--m-Ttoluidine Ethyl"esterofi lwp carboxyethyl N- (3, 3 tlifiuoron-butynaniune 1 n Ethyl ester-of N -"l3 carboxyethyl l l (3lii diflubron-butyl m chloroaiiiline I Ethyl ester of .N fl-carboxyethyl-N-difiuoromethylaniline By the use of an equivalent gram molecular Weight of thecmethyl ester o'f'N fl-carboxyethylaniline for theeth-yl esterof Necarboxyethylaniline df'theexamp1e;tneeorrespondingmetn l ester compounds can he'c prepared.

Example 15.-N 'y ketobdtyl N-difluoroethylaniline CHzCHFa 16 gramsof N-Y-ketobutylanilina'15.1 grams of difiuoroethylbromide"aridfi grams of sodium carbonateiare placed in aisuitable reaction'vess'el land heated under. refluxing. conditions iuntilicarbon dioxide ceases to. betevel vedr Upon :c'ooling, tl'ie reaction mixture l is. extracted with ieth yl a1- ic'dhol and -=-.the..ethyl. alcohol'rextract is ff-raction- -.ate'd.under (reducedpressure (3 mm., for example) ithylaniline.

Using the procedure described in Example 5,

the following compounds are readily prepared:

N 'y ketobutyl N difluoroethyl-o-toluidine N Y ketobutyl N difluoroethyl m anisidine N v ketobutyl N difiuoroethyl m chloroaniline N 7 ketobutyl N difluoroethyl m fluoroaniline N 'y ketobutyl N difiuoroethyl 2 methoxy-5-methy1aniline N Y ketobutyl N difluoroethyl 2 methoxy-5-acetaminoaniline N-fl-ketopropyl-N-difluoroethylaniline N-fi-ketobutyl-N-difluoroethylaniline N-Y -ketoamyl-N- difiuoroethylaniline N 'y ketobutyl N (2,2 difluoro n-propyl) aniline N p3 ketopropyl N (2,2-difluoro n-propyl) m-toluidine N 'y ketobutyl N (3,3 difluoro n-butyl) aniline N 5 ketopropyl N (3,3 difiuoro n-butyl) m-toluidine Example 1 6.-N- (6,6,6-trz'fluorohexyl) -N- difluoroethylaniline 28 grams of chlorobenzene, 170 grams of 6,6,6- trifiuorohexylamine, 300 cc. of water, 0.25 gram of copper powder and 0.25 gram of cuprous oxide are heated together in a copper-lined shaking autoclave at 220-225 C. for 24 hours with shaking. When cool, the contents of the autoclave are removed and extracted with benzene. After drying, the benzene extract is fractionally distilled under reduced pressure to recover N-(6,6,6-

10 annueronexyn annme a'ri'd urireacted fiidfitrinuerohexylamine. 156 "grams or 5T55 trifiubr0- amyiamine ean 'be substituted lor the ezeie trifiuero'hexylamine of the example to 4obtai11' N- "(5552B uinn-creamy: aniline. 2 3 gram's=-lof N" tcpgo-triuuoronex-yi) aniline, 415:1 *1 grams: moi di'fluoroethylbrom-ide "rand a6 iiigrams offi so'dium carbpnate are placedumaasuitable reactionwessel and heated undernflefluxing-iconditions untilzcambon dioxidezceases to be evolved. he reaction 'prodire is extliacted with thyl aalcdholand (the ellh-yl alconol extraet Li's 'Jfractionated :under aredujced" res'sure -(i2 inm., -ror cexample) .to'zgivee'a good yild of N 61616 tr ifluorohexyl N-idifiumioethylaniline. iinllarly, byithe use of 21.7 grams '"df N-'fi 1 dfluomamyl) -ani1 ine din zthe :folegoing reaction,=iN-(5;5 ;5=trifluoroamyl)aNedifluoroethyianilineioambe obtained. 1 v

Using the procedure described 'hereinbefiore, the fdllowing compounds are readilylprepared.

IIt .W'ilfbe .understoodflthat the foregoing. examples are intended "toibe "illustrative and not "lin'iitative' .d'f my in'vention; fTo illustrateftlie'cdmpounds of "Example 2 can jbe treated in "accordance lvvithithe proceduredescribed hereintc intro- "duce a second group iiitotheamino'jgroup. ITh'us, thefollowing compounds can be'r'eadily'prepared:

N-fi-hydroxypropyl-N-difluoroethyl- 4 -nitroaniline N-'y-hydroxypropyl-Ndifluoroethyl- 4 -nitroaniline N-p -dihydroxypropyl-N-difiuoroethyl- 4 -nitroaniline N-4,5-dihydroxyamyl-N-diflu0roethyl-4-nitroaniline N,N-di- (difiuoroethyl) -4-nitroaniline N-2,2-difluoroethyl-N-trifluoroethy1- 4 -m'tr0aniline N-3,3-difluoro-n-propyl N trifluoroethyl-l-nitroaniline N-fl-methoxyethyl N difluoroethyl-4-nitroaniline N-fi-ethoxyethyl-N-difiuoroethyll-nitroaniline N-Bcarboxyethyl-N-difiuoroethyl-4-nitroaniline Methyl ester of N-fl-carboxyethyl-N-difluoroethyll-nitroaniline Ethyl ester of N 8carboxyethyl-N-difiuoroethyl- 4-nitroaniline The difluoroethyl group present in each of the compounds above named can be replaced by the other difluoroalkyl groups disclosed herein and these compounds as well as the compounds resulting from the reduction of the nitro group, of the compounds under discussion, to an amino group, as illustrated in Example 3, for example, are included within the scope of my invention.

As previously indicated the compounds of the invention are useful in the preparation of azo dye compounds. Thus compounds capable of coupling can be coupled with 'diazotized aromatic compounds to form azo dyes. Aromatic amines that can be employed include, for example,

pvnitroaniline, o-chloro-p nitroaniline, o-bromop-nitroaniline, o-cyano-p-nitroaniline, o-chloroaniline, p-aminoacetophenone and 2,4-dinitrofi-chloroaniline.

coloration of cellulose organic esters, especially cellulose acetate, and nylon. Thus the dye formed by coupling diazotized p-nitroaniline with N-difiuoroethylaniline colors cellulose acetate and nylon textile materials red shades while that from diazotized o-chloro-p-nitroaniline and N-fl-hydroxyethyl- N difiuoroethyl-m-toluidine colors cellulose acetate and, nylon textile, materials rubine shades. The dye formed from (119.20- tized p-aminoacetophenone and N-di-fluoroethyl-m-toluidine colors cellulose acetate and nylon textile materialsorange shades.

Compounds of my invention containing a diazotizable free amino group can be diazotized and coupled with -p-cresol, N-(di-p-hydroxyethyl) aniline, N fin dihydroxypropyl 'm toluidine and N-B-hydroxyethyl-m-chloroaniline, for example, to obtain dye compounds which color cellulose acetate and nylon textile materials. To illustrate, the dye compoundformed by coupling diazotized N-difiuoroethyl-p-phenylenediamine with p-cresol or that formed by coupling diazotized N-,9-hydroxyethyl-N-difiuoroethyl-pphenylenediamine with N-(di-c-hydroxyethyl) aniline color cellulose acetate and nylon textile materials yellow shades. Similarly, the dye compounds formed by coupling these last two named diazotized compounds with dimethyldihydrm.

terials red shades.

Monocyclic aminobenzene compounds'containing a nuclear amino group which is substituted 12 withan aliphatic hydrocarbon, group having a trifiuorinated carbon atom are described and claimed .in my copending application, Ser. No.

624,942 filed October 26, 1945.

I claim: I 1. A compound selected from the group, of

compounds consisting of N-fi-hydroxyethyl-N- 2,2-difluoroethylaniline, and N-B,'vdihydroxypropyl-N-2,2-difiuoroethyl-m-toluidine.

2. The compound having the formula:

OH|CH2OH OHaCHFi 3. The compound having the formula: A I .omononongon JOSEPH B. DICKEY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 209,089 Switzerland June 17, 1940 

1. A COMPOUND SELECTED FROM THE GROUP OF COMPOUNDS CONSISTING OF N-B-HYDROXYETHYL-N2,2-DIFLUOROETHYLANILINE, AND N-B,$-DIHYDROXYPROPYL-N-2,2-DIFLUOROETHYL-M-TOLUIDINE. 